CN103102489A - Thermoplastic polyimide resin and preparation method thereof - Google Patents
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Abstract
The invention discloses a thermoplastic polyimide resin and a preparation method thereof. The polyimide resin has the following repeat structural units, and R represents a dianhydride residue. The thermoplastic polyimide resin prepared by the invention can be used at 200 DEG C for a long time; raw materials for synthesis of the resin are low-cost and easily available. The obtained resin powder can be easily dissolved in a solvent with low boiling point for processing, and can also be subjected to injection molding or molding pressing shaping at 300 DEG C, and has ideal mechanical properties.
Description
Technical field:
The invention belongs to the technical field of macromolecular material, relate to a kind of thermoplastic polyimide resin and preparation method thereof, described thermoplastic polyimide resin contains the new diamine monomer.
Technical background:
Polyimide (PI) is with high temperature resistant, low temperature resistant, anti-solvent, the radiation resistance of its excellence, outstanding mechanical strength and dielectric properties etc. are subject to people's great attention, have been widely used in many high-technology fields such as space flight, aviation, space, automobile, electronics, electrical equipment.But machine-shaping difficulty and manufacturing cost height are two key factors of its fast development of restriction always.Development and exploitation melt-processable and soluble thermoplastic polyimide are one of main method of improving polyimide material processing characteristics, reduction manufacturing cost.
Many polyimide materials although its backbone structure is linearity, do not have the common due thermoplasticity of linear polymer, and this is mainly to be caused by the rigid structure of its main chain and strong interaction.These have the polyimide material of linear structure, even be heated to decomposition temperature, also can not show the melt-flow behavior, and even ruckbildung can not occur.Thermoplastic polyimide of the present invention refers to have good melting behaviour and solvability, the polyimide that can adopt mold pressing, extrude, the plastics molding process method of the routine such as injection is carried out machine-shaping.
20th century 70 are to the eighties, NASA (NASA) has at first carried out the research work of high-performance high-temperature resistance adhesive, be intended to development can be under hot conditions (200～300 ℃) organic adhesion agent of using continuously, the structure unit that is used for the space flight and aviation aircraft, and thermoplastic polyimide resin is exactly one of emphasis of its research.Compare with the Thermocurable polyimide material, thermoplastic polyimide resin have good toughness, damage tolerance large, many advantages such as can repair, also can be used as the matrix resin that continuous carbon fibre strengthens polymer matrix composites, prepared prepreg does not need cryopreservation, can obviously reduce the matrix material manufacturing cost, improve the impelling strength of matrix material etc.On this basis, people further develop again directly melt-processed, as mold pressing, extrude, injection molding thermoplastic polyimide material.
Adopting melt molding technique to make the thermoplastic polyimide goods not only can the decrease cost, enhance productivity, and stabilized product quality, but also can make the high value added product with property and function.In addition, thermoplastic polyimide does not need solvent usually in the melt molding process, and without organic volatile part, environmental pollution is little.
Although common thermoplastic polyimide resin melt-processable, but compare with traditional thermoplastic, polymeric materials, also there is certain difference, main manifestations is: the melt-flow behavior of thermoplastic polyimide resin only shows being subjected in thermal process of first or limited number of times, after heating through first or limited number of times, its melt-flow behavior is just basic or completely lose.Major cause may for, softening or the melt temperature of thermoplastic polyimide resin is higher (〉 250 ℃ usually), and its processing temperature (requiring melt to have very low viscosity and good mobility at this temperature) is usually up to 300～425 ℃.Under such hot conditions, aromatic polymer may produce crosslinked, and its most general mechanism explain is that under high temperature, the aromatic ring dehydrogenation forms radical, and is this crosslinked with producing between the aromatic ring of radical.Therefore, thermoplastic polyimide resin can only carry out the melt-processed of limited number of times (even for once) usually, therefore there is the people that this base polymer is become the pseudo-heat thermoplastic polymer.Nonetheless, thermoplastic polyimide resin has still obtained people's approval with its excellent over-all properties, occupy in some important technical field the status of not replacing.Therefore, development, exploitation have the thermoplastic polyimide material that can repeatedly repeat melt-processable and become one of study hotspot in recent years.
Analyze from the chemical structure of polymkeric substance, the factor that affects the thermoplastic polyimide melt-processable mainly comprises: molecular weight and the molecular weight distribution of (1) polymkeric substance; (2) rigidity of main polymer chain structure and regularity; (3) aggregated structure of polymkeric substance etc.
The molecular weight of thermoplastic polyimide resin and molecular weight distribution have direct impact to its melt processability.Molecular weight is too low affects mechanical property and thermotolerance, and too high its melt processability that affects of molecular weight.Generally speaking, the more wide melt that more is conducive to of molecular weight distribution.Research structure shows, the number-average molecular weight of thermoplastic polyimide resin can be taken into account mechanics and the resistance toheat of melt-processable and material in the scope of 10000～50000g/mol.
The main chain chemical structure of systematic study polyimide and the relation of interdependence of its performance are the bases of developing thermoplastic polyimide.The preparation method who grasps the high-performance thermoplastic polyimide material not only has huge economic interests, has simultaneously important scientific meaning.
Summary of the invention
Main purpose of the present invention is to provide a kind of thermoplastic polyimide resin.
Another object of the present invention is to provide a kind of preparation method of thermoplastic polyimide resin.
Purpose of the present invention is achieved through the following technical solutions:
The solvable polyimide resin of a kind of thermoplasticity, it is that described polyimide resin has following repeated structural unit:
In formula
Represent the dianhydride residue.
The weight-average molecular weight of above-mentioned polyimide resin is 8000 ~ 300000; Be preferably: 10000 ~ 200000; More preferably 10000 ~ 100000; Further be preferably 10000 ~ 50000.
The solvable polyimide resin of above-mentioned thermoplasticity, it is
The dianhydride residue of representative is selected from:
(1) full aromatic dianhydride
(2) bridging aromatic dianhydride
Wherein one or more;
Be preferably:
Above-mentioned thermoplastic polyimide resin, adopt the following steps preparation:
The first step: with strong polar non-proton organic solvent, diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, under mechanical stirring, the inflated with nitrogen protective reaction is 4 ~ 24 hours, obtains thick polyamic acid solution;
Second step: with the polyamic acid solution of gained directly pour into pour ethanol into after gel in ethanol becomes solid or add the catalyzer of catalytic amount under whipped state in gel become solid, and soaked 24 ~ 48 hours, wash 1 time every 12 hours with ethanol therebetween, solid after soaking is centrifugal, and oven dry under 80 ~ 120 ℃, then pulverize, the heating cyclisation: 70 ~ 90 ℃ are incubated 1 ~ 3 hour, again take 20 ~ 50 ℃ as a ladder, be warmed up to 200 ~ 300 ℃, each ladder was kept 1 ~ 120 minute, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
The structural formula of above-mentioned described diamine monomer is:
The preparation method of above-mentioned thermoplastic polyimide resin comprises the following steps:
The first step: with strong polar non-proton organic solvent, diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, under mechanical stirring, the inflated with nitrogen protective reaction is 4 ~ 24 hours, obtains thick polyamic acid solution;
Second step: with the polyamic acid solution of gained directly pour into pour ethanol into after gel in ethanol becomes solid or add the catalyzer of catalytic amount under whipped state in gel become solid, and soaked 24 ~ 48 hours, wash 1 time every 12 hours with ethanol therebetween, solid after soaking is centrifugal, and oven dry under 80 ~ 120 ℃, then pulverize, the heating cyclisation: 70 ~ 90 ℃ are incubated 1 ~ 3 hour, again take 20 ~ 50 ℃ as a ladder, be warmed up to 200 ~ 300 ℃, each ladder was kept 1 ~ 120 minute, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
The preparation method of above-mentioned thermoplastic polyimide resin, it is: strong polar non-proton organic solvent used is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, described catalyzer is any one or two kinds in acetic acid and triethylamine, and being preferably weight ratio is the acetic acid of 1:0.5 ~ 1.5 and the mixture of triethylamine.The consumption of described catalyzer is: the proportionlity of catalyzer and diamine monomer and dianhydride monomer quality sum is preferably 1:1 ~ 5.
The preparation method of above-mentioned thermoplastic polyimide resin, it is: the solid content of described polyamic acid solution is 10% ~ 60%.
The preparation method of above-mentioned thermoplastic polyimide resin, it is, the molar ratio of described diamine monomer and dianhydride monomer is 1:1 ~ 1:1.2.
The preparation method of above-mentioned thermoplastic polyimide resin, its structural formula that is described diamine monomer is:
Described dianhydride monomer is any one or a few in following compound:
Room temperature described in the present patent application file is 17 ~ 25 ℃.
Beneficial effect of the present invention:
The thermoplastic polyimide resin of the present invention's preparation can be at 200 ℃ of life-time service, the starting monomer cost of synthetic this resin is low, be easy to get, and the resin-oatmeal that obtains both can be easy to be dissolved in is convenient to processing in the lower solvent of boiling point, again can injection moulding or mold pressing machine-shaping at the temperature below 300 ℃, and have more satisfactory mechanical property.
But thermoplastic polyimide resin presoma polyamic acid of the present invention both heating ring changes into the polyimide resin powder, also can obtain the more shallow rete of color as liquid coating, and table 1 is the salient features of polyamic acid.
The salient features of table 1 polyamic acid
| Performance | Index |
| Solid content (wt%) | 10~60 |
| Color | Brown |
| 20 ℃ of kinematic viscosity (cP) | 2000~250000 |
| Package stability (0 ~ 5 ℃) | 20 ~ 30 days |
The mould pressing process of the thermoplastic polyimide resin powder of the present invention preparation in can employing table 2 is processed into the goods such as sheet material or bar.
Table 2 thermoplastic polyimide powder mould pressing process
| The operation title | Temperature (℃) | Pressure (MPa) | Time (min) |
| Section heats up | 150～200 | 15~25 | 20~90 |
| The |
200 | 15~25 | 20~90 |
| Section heats up | 200～260 | 15~25 | 20~90 |
| Profiled section | 260 | 15~25 | 20~90 |
| Temperature descending section | 260～200 | ―― | Fixed depending on cooling method |
The thermoplastic polyimide resin of the present invention's preparation has the fundamental property shown in table 3.
The performance of table 3 thermoplastic polyimide resin
| Project | Testing standard or instrument | Unit | Result | |
| Outward appearance | - | - | Pale yellow powder | |
| Granularity | | Order | 200 or 500 | |
| Real density | GB1033-1970 | kg/m 3 | 1350 | |
| Water-intake rate (25 ℃, 24Hrs) | GB1034-1970 | % | ≤0.2 | |
| Molding shrinkage (25～340 ℃) | - | % | 0.8 | |
| Tensile strength (20 ℃) | GB/T1040-1992 | MPa | 100 | |
| Elongation (20 ℃) | GB/T1040-1992 | % | 18 | |
| Flexural strength (20 ℃) | GB1042-1979 | |
150 | |
| Compressive strength (20 ℃) | GB/T1041-1992 | MPa | 3500 | |
| Simple beam impact strength (non-notch) | GB/T16420-1996 | kJ/m 2 | 130 | |
| Tg(N2,?10℃/min) | DSC(DSC204/1/F) | ℃ | 223 | |
| Td5(Air,?10℃/min) | TGA(STA449C/6/F) | ℃ | 400 | |
| Dielectric strength | GB1408-1978 | kV/mm | 460 | |
| Specific inductivity (1MHz, 20 ℃) | GB1409-1978 | － | 3.2 | |
| Dielectric loss (1MHz, 20 ℃) | GB1409-1978 | － | 1.0×10 -4 | |
| Surface resistivity | GB1410-1978 | Ω | 1.8×10 14 | |
| Volume specific resistance | GB1410-1978 | Ω·cm? | 5.1×10 16 | |
| Solubleness (DMF, NMP) | g | 80 |
Outside order, the solution of thermoplastic polyimide resin powder of the present invention can be filmed on sheet glass, and the heating desolvation can make uniform transparent film, and the UV, visible light light transmission cutoff wavelength of measuring this film is 392nm, maximum transmission is about 75% at 800 ~ 850nm place.
Description of drawings
Fig. 1 is the m-BAPS/PMDA PI polyimide DSC curve of embodiment 1 and embodiment 2 preparations.
Fig. 2 is the m-BAPS/ODPA PI polyimide DSC curve of embodiment 5 and embodiment 6 preparations.
Fig. 3 is the m-BAPS/PMDA PI polyimide infrared spectra of embodiment 1 and embodiment 2 preparations.
Fig. 4 is the m-BAPS/ODPA PI polyimide infrared spectra of embodiment 5 and embodiment 6 preparations.
Embodiment:
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in 10.3076 gram N are housed; in the polyreaction bottle of N-N,N-DIMETHYLACETAMIDE; mechanical stirring; add 0.8725 gram (0.004 mole) pyromellitic acid dianhydride (PMDA) after the dissolving fully, inflated with nitrogen protection continued stirring reaction 12 hours in batches, obtained solid content and be 20% polyamic acid solution.
The polyamic acid solution of gained is poured in ethanol, gel becomes solid, and soaked 24 hours, wash 1 time every 12 hours with ethanol therebetween, the solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize, the heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, then naturally cooling, last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of transparent polyimide film is as follows:
Recording second-order transition temperature is 269 ℃.Polymer average molecular weight M
wBe 20000.
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in 10.3076 gram N are housed; in the polyreaction bottle of N-N,N-DIMETHYLACETAMIDE; mechanical stirring; add 0.8725 gram (0.004 mole) pyromellitic acid dianhydride (PMDA) after the dissolving fully, inflated with nitrogen protection continued stirring reaction 12 hours in batches, obtained solid content and be 20% polyamic acid solution.
Polyamic acid solution adds 1g aceticanhydride, 0.8g triethylamine under whipped state, stir after 1 hour that gel obtains solid in ethanol, and soaks 24 hours, therebetween with ethanol every washing in 12 hours 1 time.Solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverizes, the heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, then naturally cooling, last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 270 ℃.Polymer average molecular weight M
wBe 25000.
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in the polyreaction bottle that 11.5252 gram N,N-dimethylacetamide are housed, mechanical stirring; add 1.1769 grams (0.004 mole) 3 after the dissolving fully in batches; 3', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA); inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
The polyamic acid solution of gained is poured in ethanol, gel becomes solid, and soaked 24 hours, wash 1 time every 12 hours with ethanol therebetween, the solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize, the heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, then naturally cooling, last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 235 ℃.Polymer average molecular weight M
wBe 30000.
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in the polyreaction bottle that 11.5252 gram N,N-dimethylacetamide are housed, mechanical stirring; add 1.1769 grams (0.004 mole) 3 after the dissolving fully in batches; 3', 4,4'-biphenyl tetracarboxylic dianhydride (BPDA); inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
Polyamic acid solution adds 1g aceticanhydride, 0.8g triethylamine under whipped state, stir after 1 hour that gel obtains solid in ethanol, and soaked 24 hours, therebetween with ethanol every washing in 12 hours 1 time, solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 238 ℃.Polymer average molecular weight M
wBe 36000.
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in 11.778 gram N are housed; in the polyreaction bottle of N-N,N-DIMETHYLACETAMIDE; mechanical stirring adds 1.2401 grams (0.004 mole) 4,4'-Biphenyl Ether dianhydride (ODPA) after the dissolving fully in batches; inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
The polyamic acid solution of gained is poured in ethanol, gel becomes solid, and soaked 24 hours, wash 1 time every 12 hours with ethanol therebetween, the solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize, the heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, then naturally cooling, last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 223 ℃.Polymer average molecular weight M
wBe 20000.
Embodiment 6
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in 11.778 gram N are housed; in the polyreaction bottle of N-N,N-DIMETHYLACETAMIDE; mechanical stirring adds 1.2401 grams (0.004 mole) 4,4'-Biphenyl Ether dianhydride (ODPA) after the dissolving fully in batches; inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
Polyamic acid solution adds 1g aceticanhydride, 0.8g triethylamine under whipped state, stir after 1 hour that gel obtains solid in ethanol, and soaked 24 hours, therebetween with ethanol every washing in 12 hours 1 time, solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 225 ℃.Polymer average molecular weight M
wBe 26000.
Embodiment 7
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in the polyreaction bottle that 11.9732 gram N,N-dimethylacetamide are housed, mechanical stirring; add 1.2889 grams (0.004 mole) 3 after the dissolving fully in batches; 3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA); inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
The polyamic acid solution of gained is poured in ethanol, gel becomes solid, and soaked 24 hours, wash 1 time every 12 hours with ethanol therebetween, the solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize, the heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, then naturally cooling, last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 224 ℃.Polymer average molecular weight M
wBe 20000.
At room temperature; with 1.7044 grams (0.004 mole) 4; two (3-amino-benzene oxygen) sulfobenzides (m-BAPS) of 4'-are dissolved in the polyreaction bottle that 11.9732 gram N,N-dimethylacetamide are housed, mechanical stirring; add 1.2889 grams (0.004 mole) 3 after the dissolving fully in batches; 3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA); inflated with nitrogen protection continued stirring reaction 12 hours, obtained solid content and be 20% polyamic acid solution.
Polyamic acid solution is added 1g aceticanhydride, 0.8g triethylamine at whipped state, stir after 1 hour that gel obtains solid in ethanol, and soaked 24 hours, therebetween with ethanol every washing in 12 hours 1 time, solid after immersion is centrifugal, and oven dry under 110 ℃, then pulverize heating cyclisation: kept 2 hours for 80 ℃, ladder-elevating temperature to 110 ℃, 140 ℃, 170 ℃, 200 ℃, 230 ℃, each ladder was respectively kept 30 minutes, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
In the present embodiment, the molecular structure of polyimide resin is as follows:
Recording second-order transition temperature is 230 ℃.Polymer average molecular weight M
wBe 26000.
Claims (10)
1. solvable polyimide resin of thermoplasticity is characterized in that described polyimide resin has following repeated structural unit:
In formula
Represent the dianhydride residue.
2. thermoplastic polyimide resin according to claim 1, the weight-average molecular weight that it is characterized in that described polyimide resin is 8000 ~ 300000; Be preferably: 10000 ~ 200000.
3. the solvable polyimide resin of thermoplasticity according to claim 1, is characterized in that
The dianhydride residue of representative is selected from:
(1) full aromatic dianhydride
(2) bridging aromatic dianhydride
Wherein one or more;
Be preferably:
4. any one described thermoplastic polyimide resin according to claim 1 ~ 3 is characterized in that adopting the following steps preparation:
The first step: with strong polar non-proton organic solvent, diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, under mechanical stirring, the inflated with nitrogen protective reaction is 4 ~ 24 hours, obtains thick polyamic acid solution;
Second step: with the polyamic acid solution of gained directly pour into pour ethanol into after gel in ethanol becomes solid or add the catalyzer of catalytic amount under whipped state in gel become solid, and soaked 24 ~ 48 hours, wash 1 time every 12 hours with ethanol therebetween, solid after soaking is centrifugal, and oven dry under 80 ~ 120 ℃, then pulverize, the heating cyclisation: 70 ~ 90 ℃ are incubated 1 ~ 3 hour, again take 20 ~ 50 ℃ as a ladder, be warmed up to 200 ~ 300 ℃, each ladder was kept 1 ~ 120 minute, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
5. thermoplastic polyimide resin according to claim 4 is characterized in that the structural formula of described described diamine monomer is:
6. the preparation method of thermoplastic polyimide resin claimed in claim 1 is characterized in that comprising the following steps:
The first step: with strong polar non-proton organic solvent, diamine monomer is dissolved in the polyreaction bottle fully, dianhydride monomer is added in batches, under mechanical stirring, the inflated with nitrogen protective reaction is 4 ~ 24 hours, obtains thick polyamic acid solution;
Second step: with the polyamic acid solution of gained directly pour into pour ethanol into after gel in ethanol becomes solid or add the catalyzer of catalytic amount under whipped state in gel become solid, and soaked 24 ~ 48 hours, wash 1 time every 12 hours with ethanol therebetween, solid after soaking is centrifugal, and oven dry under 80 ~ 120 ℃, then pulverize, the heating cyclisation: 70 ~ 90 ℃ are incubated 1 ~ 3 hour, again take 20 ~ 50 ℃ as a ladder, be warmed up to 200 ~ 300 ℃, each ladder was kept 1 ~ 120 minute, naturally cooling then, and last high speed pulverization obtains the polyimide resin powder.
7. the preparation method of thermoplastic polyimide resin according to claim 6, it is characterized in that: strong polar non-proton organic solvent used is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, described catalyzer is any one or two kinds in acetic acid and triethylamine, and being preferably weight ratio is the acetic acid of 1:0.5 ~ 1.5 and the mixture of triethylamine.
8. the preparation method of thermoplastic polyimide resin according to claim 6, it is characterized in that: the solid content of described polyamic acid solution is 10% ~ 60%.
9. the preparation method of thermoplastic polyimide resin according to claim 6, is characterized in that, the molar ratio of described diamine monomer and dianhydride monomer is 1:1 ~ 1:1.2.
10. the preparation method of according to claim 6 or 9 described thermoplastic polyimide resins is characterized in that the structural formula of described diamine monomer is:
，
Described dianhydride monomer is any one or a few in following compound:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9416229B2 (en) | 2014-05-28 | 2016-08-16 | Industrial Technology Research Institute | Dianhydride and polyimide |
| CN113429623A (en) * | 2021-06-17 | 2021-09-24 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by degrading polyimide resin |
| WO2021226951A1 (en) * | 2020-05-14 | 2021-11-18 | 律胜科技股份有限公司 | Polyimide film and manufacturing method therefor |
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| CN101851331A (en) * | 2009-04-01 | 2010-10-06 | 浙江鼎龙化工有限公司 | Soluble high-performance polyimide and preparation method thereof |
| CN102807675A (en) * | 2012-08-19 | 2012-12-05 | 南京依麦德光电材料科技有限公司 | Flexible transparent polyimide film material and preparation method thereof |
| CN102911359A (en) * | 2012-10-19 | 2013-02-06 | 中国科学院宁波材料技术与工程研究所 | Transparent polyimide and preparation method thereof |
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| US9416229B2 (en) | 2014-05-28 | 2016-08-16 | Industrial Technology Research Institute | Dianhydride and polyimide |
| WO2021226951A1 (en) * | 2020-05-14 | 2021-11-18 | 律胜科技股份有限公司 | Polyimide film and manufacturing method therefor |
| CN113429623A (en) * | 2021-06-17 | 2021-09-24 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by degrading polyimide resin |
| CN113429623B (en) * | 2021-06-17 | 2022-05-31 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by degrading polyimide resin |
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